Production of broad molecular weight polyethylene

ABSTRACT

The present invention is directed to the use of aluminum alkyl activators and co-catalysts to improve the performance of chromium-based catalysts. The aluminum alkyls allow for the variable control of polymer molecular weight, control of side branching while possessing desirable productivities, and may be applied to the catalyst directly or separately to the reactor. Adding the alkyl aluminum compound directly to the reactor (in-situ) eliminates induction times.

CROSS-REFERENCE TO RELATED APPLICATION

The present application is a divisional of U.S. patent application Ser.No. 10/716,291, filed Nov. 18, 2003, now issued as U.S. Pat. No.6,989,344, which claims priority to Provisional U.S. Patent ApplicationSer. No. 60/436,790 filed Dec. 27, 2002, and are herein incorporated byreference.

TECHNICAL FIELD

The present invention relates to the use of chromium-based catalystswith aluminum alkyl activators. The aluminum alkyls allow for thecontrol of polymer molecular weight, molecular weight distribution, andside-chain branching while possessing desirable productivities. Thealuminum alkyls may be applied to the catalyst directly or separately tothe reactor.

BACKGROUND OF THE INVENTION

Ethylene polymers have been used generally and widely as resin materialsfor various molded articles and are required of different propertiesdepending on the molding method and purpose. For example, polymershaving relatively low molecular weights and narrow molecular weightdistributions are suitable for articles molded by an injection moldingmethod. On the other hand, polymers having relatively high molecularweights and broad molecular weight distributions are suitable forarticles molded by blow molding or inflation molding. In manyapplications, medium-to-high molecular weight polyethylenes aredesirable. Such polyethylenes have sufficient strength for applicationswhich call for such strength (e.g., pipe applications), andsimultaneously possess good processability characteristics.

Ethylene polymers having broad molecular weight distributions can beobtained by use of a chromium catalyst obtained by calcining a chromiumcompound carried on an inorganic oxide carrier in a non-reducingatmosphere to activate it such that at least a portion of the carriedchromium atoms is converted to hexavalent chromium atoms (Cr+6) commonlyreferred to in the art as the Phillips catalyst. The respective materialis impregnated onto silica, fluidized and heated in the presence ofoxygen to about 400° C.-860° C., converting chromium from the +3oxidation state to the +6 oxidation state. A second chromium catalystused for high density polyethylene applications consists ofsilylchromate (bis-triphenylsilyl chromate) absorbed on dehydratedsilica and subsequently reduced with diethylaluminum ethoxide (DEALE).The resulting polyethylenes produced by each of these catalysts aredifferent in some important properties. Chromium oxide-on-silicacatalysts have good productivity (g PE/g catalyst), also measured byactivity (g PE/g catalyst-hr) but produce polyethylenes with molecularweight distributions lower than that desired. Silylchromate-basedcatalysts produce polyethylenes with desirable molecular weightcharacteristics (broader molecular weight distribution with a highmolecular weight shoulder on molecular weight distribution curve,indicative of two distinct molecular weight populations).

Monoi, in Japanese Patent 2002020412 discloses contain the use ofinorganic oxide-supported Cr+6-containing solid components (A) preparedby sintering under nonreducing conditions, dialkylaluminum functionalgroup-containing alkoxides (B), and trialkylaluminum (C). The resultingethylene polymers are said to possess good environmental stress crackresistance and good blow molding creep resistance. U.S. application2002/0042482 discloses a method of ethylene polymerization inco-presence of hydrogen using a trialkylaluminum compound-carriedchromium catalyst (A), wherein the chromium catalyst is obtained bycalcination-activating a Cr compound carried on an inorganic oxidecarrier in a non-reducing atmospheric to convert Cr atoms into thehexavalent state and then treating A with a trialkylaluminum compound inan inert hydrocarbon solvent and removing the solvent in a short time.

Hasebe et al. Japanese Patent 2001294612 discloses catalysts containinginorganic oxide-supported Cr compounds calcined at 300° C.-1100° C. in anonreducing atmosphere, R₃-nAlL_(n) (R=C1-12 alkyl; L=C1-8 alkoxy,phenoxy; 0<n<1), and Lewis base organic compounds. The catalysts aresaid to produce polyolefins with high molecular weight and narrowmolecular weight distribution.

Hasebe et al., in Japanese Patent 2001198811 discloses polymerization ofolefins using catalysts containing Cr oxides (supported on fireresistant compounds and activated by heating under nonreductiveconditions) and R₃-nAlL_(n) (R=C1-6 alkyl; L=C1-8 alkoxy, phenoxy; n>0.5but <1). Ethylene is polymerized in the presence of SiO₂-supported CrO₃and a reaction product of a 0.9:1 MeOH-Et₃Al mixture to give a polymerwith melt index 0.18 g/10 min at 190° under 2.16-kg load and 1-hexenecontent 1.6 mg/g-polymer.

Da, et al, in Chinese Patent 1214344 teaches a supported chromium-basedcatalyst for gas-phase polymerization of ethylene prepared byimpregnating an inorganic oxide support having hydroxyl group on thesurface with an inorganic chromium compound aqueous solution; drying inair; activating the particles in oxygen; and reducing the activatedcatalyst intermediate with an organic aluminum compound. 10 g commercialsilica gel was mixed with 0.05 mol/L CrO₃ aqueous solution, dried at80-120° C. for 12 h, baked at 200° C. for 2 h and 600° C. for 4 h,reduced with 25% hexane solution of diethylethoxyaluminum to give powdercatalyst with Cr content 0.25% and Al/Cr ratio of 3.

Durand, et al, U.S. Pat. No. 5,075,395, teaches a process forelimination of the induction period in the polymerization of ethylene bybringing ethylene in contact under fluidized-bed polymerizationconditions and/or stirred mechanically, with a charge powder in thepresence of a catalyst comprising a chromium oxide compound associatedwith a granular support and activated by thermal treatment, thiscatalyst being used in the form of a prepolymer. The Durand process ischaracterized in that the charge powder employed is previously subjectedto a treatment by contacting the said charge powder with anorganoaluminium compound, in such a way that the polymerization startsup immediately after the contacting of the ethylene with the chargepowder in the presence of the prepolymer.

Unique to chromium-based catalysis generally, molecular weights increaseas residence time of the reaction increases. Thus, increasing residencetime allows one to achieve higher molecular weight polymers fromchromium oxide-based catalysts. However, an increase in reactorresidence time represents a decrease in reactor throughput and anincrease in production costs. Lowering residence times may lead tobetter economics but for any particular chromium-based catalyst, alsolead to lower polymer molecular weights. To help preserve highermolecular weights, one may decrease reactor temperature, but thisresults in reduced heat transfer and lower production rates. Bettercontrol of the characteristics of the resulting polyethylene, whilesimultaneously preserving or improving productivity is desired inchromium-based catalyst systems. It is desirable to preserve desirablemolecular weights and catalyst activities with decreased residencetimes. While the prior art contains these and other examples of the useof Phillips-type catalysts and an organoaluminum compound incombination, there has not yet been disclosed a method for obtaining apolyethylene having moderate-to-high molecular weight using a catalystsystem having good productivity and in which the molecular weight andmolecular weight distribution may be tuned and side chain branching maybe controlled. Additionally, the prior art is devoid of any teaching ofthe use of the in-situ addition of aluminum alkyls (directly to thereactor) to comprehensively address the problems encountered with higherreactor throughput and shorter residence time (polymer molecular weight,molecular weight distribution and catalyst productivity). The presentinvention addresses a number of the shortcomings of chromium-basedethylene polymerization not previously addressed in the prior art.

BRIEF SUMMARY OF THE INVENTION

The present invention is directed to a system and method for thepolymerization of ethylene that can be used for high space time yieldoperation (shorter residence times) employing chromium-based catalyststhat have good productivities and variable control of polymer molecularweight, molecular weight distribution, and side chain branch formation.

As used herein, “a” or “an” is defined herein as one or more.

As used herein, “in situ”, in reference to the mode of addition of acomponent to the catalyst, is defined herein as addition to the catalystin the reactor. Therefore, when a catalyst component is added in situ,it is added to the remaining catalyst components in the reactor and isnot combined with the other catalyst components prior to their transportto the reactor. “In reactor” is synonymous with and used interchangeablyherein with “in situ.”

As used herein, “in catalyst” or “on catalyst”, in reference to the modeof addition of a component to the catalyst, is defined herein asaddition directly to the catalyst prior to introduction of the catalystto the reactor. Therefore, when a component is added to the catalyst “incatalyst” or “on catalyst”, it is added to the other catalyst componentsprior to the transport of the aggregate to the reactor.

As used herein, the term alkyl aluminum is defined as a compound havingthe general formula R₃Al wherein R can be any of one to twelve carbonalkyl groups. The R groups can be the same or different.

As used herein, the term alkyl aluminum alkoxide is defined as acompound having the general formula R₂—Al—OR wherein R can be any of oneto twelve carbon alkyl groups and OR is a one to twelve carbon alkoxy orphenoxy group. The R groups can be the same or different.

As used herein, “DEALE” means diethyl aluminum ethoxide.

As used herein, “TEAL” means triethyl aluminum.

As used herein, “TEB” means triethyl boron.

As used herein, “TIBA” means tri-isobutyl aluminum.

As used herein, “TNHAL” means tri-n-hexyl aluminum.

As used herein, “M_(w)” is the weight-average molecular weight.

As used herein, “M_(n)” is the number-average molecular weight.

As used herein, “M_(z)” is the z-average molecular weight.

As used herein, “molecular weight distribution” is equal to M_(w)/M_(n).

In one embodiment of the present invention, there is a supportedchromium catalyst comprising chromium oxide, a silica-containing supportcomprising silica selected from the group consisting of silica having(a) a pore volume of about 1.1-1.8 cm³/g and a surface area of about245-375 m²/g, (b) a pore volume of about 2.4-3.7 cm³/g and a surfacearea of about 410-620 m²/g, and (c) a pore volume of about 0.9-1.4 cm³/gand a surface area of about 390-590 m²/g; and an organoaluminum compoundwherein the supported chromium catalyst is activated at 400-860° C. Inanother embodiment, the organoaluminum compound is added in situ. Inanother embodiment, the silica has a pore volume of about 2.4-3.7 cm³/gand a surface area of about 410-620 m²/g and the organoaluminum compoundis an alkyl aluminum alkoxide compound. In another embodiment, theorganoaluminum compound is an alkyl aluminum alkoxide compound. In apreferred embodiment, the alkyl aluminum alkoxide compound is diethylaluminum ethoxide. In another embodiment, the catalyst is formed by thein situ addition of an alkyl aluminum alkoxide compound. In a preferredembodiment, the alkyl aluminum alkoxide added in situ is diethylaluminum ethoxide. In one embodiment, the supported catalyst isactivated at 600-860° C. In another embodiment the catalyst alsocomprises titanium tetraisopropoxide. In another embodiment, thecatalyst organoaluminum compound is an alkyl aluminum compound. In apreferred embodiment where the organoaluminum compound is an alkylaluminum compound, the alkyl aluminum compound is triethyl aluminum,tri-isobutyl aluminum, or tri-n-hexyl aluminum. Preferably, the alkylaluminum compound is added in situ. More preferably, the catalyst isformed by the in situ addition of the triethyl aluminum.

In another embodiment, there is a supported chromium catalyst systemcomprising silylchromate, a silica-containing support, dehydrated atabout 400-860° C., comprising silica selected from the group consistingof silica having (a) a pore volume of about 1.1-1.8 cm³/g and a surfacearea of about 245-375 m²/g, (b) a pore volume of about 2.4-3.7 cm³/g anda surface area of about 410-620 m²/g, and (c) a pore volume of about0.9-1.4 cm³/g and a surface area of about 390-590 m²/g; anorganoaluminum compound; the catalyst formed by the process of addingthe organoaluminum compound in situ. In another embodiment, theorganoaluminum compound is an alkyl aluminum alkoxide compound. In apreferred embodiment, the alkyl aluminum alkoxide compound is diethylaluminum ethoxide. In another embodiment, the organoaluminum compound isan alkyl aluminum compound. In a preferred embodiment, the alkylaluminum compound is selected from the group consisting of triethylaluminum, tri-isobutyl aluminum, and tri-n-hexyl aluminum.

In another embodiment, there is a supported chromium catalyst systemcomprising: silylchromate, a silica-containing support, dehydrated atabout 400-860° C., comprising silica selected from the group consistingof silica having (a) a pore volume of about 1.1-1.8 cm³/g and a surfacearea of about 245-375 m²/g, (b) a pore volume of about 2.4-3.7 cm³/g anda surface area of about 410-620 m²/g, and (c) a pore volume of about0.9-1.4 cm³/g and a surface area of about 390-590 m²/g; anorganoaluminum compound selected from the group consisting of triethylaluminum, tri-isobutyl aluminum, and tri-n-hexyl aluminum, the catalystbeing formed by the process of adding the organoaluminum compound incatalyst.

In another embodiment, there is a supported chromium catalyst systemcomprising silylchromate, a silica-containing support, dehydrated at400-860° C., comprising silica selected from the group consisting ofsilica having a pore volume of about 0.9-1.4 cm³/g and a surface area ofabout 390-590 m²/g; and, an organoaluminum compound.

In another embodiment, there is a supported chromium catalyst systemcomprising silylchromate, a silica-containing support, dehydrated at400-860° C., comprising silica selected from the group consisting ofsilica having (a) a pore volume of about 1.1-1.8 cm³/g and a surfacearea of about 245-375 m²/g, (b) a pore volume of about 2.4-3.7 cm³/g anda surface area of about 410-620 m²/g, and (c) a pore volume of about0.9-1.4 cm³/g and a surface area of about 390-590 m²/g; and triethylboron, formed by the process of adding the triethyl boron in situ.

In another embodiment, there is a process for producing an ethylenepolymer comprising the steps of contacting ethylene under polymerizationconditions with a catalyst system, the catalyst system comprisingchromium oxide, an alkyl aluminum, and a silica-containing supportcomprising silica selected from the group consisting of silica having(a) a pore volume of about 1.1-1.8 cm³/g and a surface area of about245-375 m²/g, (b) a pore volume of about 2.4-3.7 cm³/g and a surfacearea of about 410-620 m²/g, and (c) a pore volume of about 0.9-1.4 cm³/gand a surface area of about 390-590 m²/g; and, controlling one or moreof catalyst activity, polymer side chain branching, polymer M_(z)/M_(w),polymer M_(w)/M_(n), polymer density and polymer molecular weight of theresulting ethylene polymer by the addition of alkyl aluminum alkoxide inan amount to effect a final ratio of equivalents of aluminum toequivalents of chromium of from 0.1:1 to 10:1. In another embodiment thealkyl aluminum is triethyl aluminum, tri-isobutyl aluminum, ortri-n-hexyl aluminum. In a preferred embodiment, the alkyl aluminumalkoxide is diethyl aluminum ethoxide. In another embodiment, thecatalyst system further comprises titanium tetraisopropoxide. In apreferred embodiment, the polymerization is gas phase polymerization. Ina preferred embodiment, the addition of diethyl aluminum ethoxidecomprises in situ addition. In another embodiment, the addition ofdiethyl aluminum ethoxide comprises addition directly to the catalystduring catalyst preparation. In another embodiment, the polymerM_(w)/M_(n) is greater than or equal to 16 and said polymer M_(z)/M_(w)is greater than or equal to 6.

In another embodiment, there is a process for producing an ethylenepolymer comprising the steps of contacting ethylene under polymerizationconditions with a catalyst system comprising silylchromate and asilica-containing support comprising silica selected from the groupconsisting of silica having (a) a pore volume of about 1.1-1.8 cm³/g anda surface area of about 245-375 m²/g, (b) a pore volume of about 2.4-3.7cm³/g and a surface area of about 410-620 m²/g, and (c) a pore volume ofabout 0.9-1.4 cm³/g and a surface area of about 390-590 m²/g; whereinsaid silica-containing support is dehydrated at about 400-860° C.; and,controlling catalyst productivity, reaction induction time and polymermolecular weight of the resulting ethylene polymer by the addition of anorganoaluminum compound in an amount to effect a final ratio ofequivalents of aluminum to equivalents of chromium of from 0.1:1 to10:1. In a preferred embodiment, the addition of an organoaluminumcompound comprises addition of diethyl aluminum ethoxide. In anotherembodiment the addition of diethyl aluminum ethoxide comprises in situaddition of diethyl aluminum ethoxide. In another embodiment, theaddition of said diethyl aluminum ethoxide comprises addition directlyto the catalyst during catalyst preparation. In a preferred embodiment,the polymerization is gas phase polymerization. Preferably, thesilylchromate is loaded onto said silica-containing support at a loadingof about 0.15-1.0 weight % of chromium. In another embodiment, theaddition of an organoaluminum compound comprises addition of an alkylaluminum compound. Preferably, the alkyl aluminum compound is selectedfrom the group consisting of triethyl aluminum, tri-isobutyl aluminum,and tri-n-hexyl aluminum.

In another embodiment, there is a process for producing an ethylenepolymer comprising the steps of contacting ethylene under polymerizationconditions with a catalyst system comprising silylchromate and asilica-containing support comprising silica selected from the groupconsisting of silica having (a) a pore volume of about 1.1-1.8 cm³/g anda surface area of about 245-375 m²/g, (b) a pore volume of about 2.4-3.7cm³/g and a surface area of about 410-620 m²/g, and (c) a pore volume ofabout 0.9-1.4 cm³/g and a surface area of about 390-590 m²/g; hereinsaid silica-containing support is dehydrated at about 400-860° C.; and,controlling catalyst activity, reaction induction time, and polymermolecular weight of the resulting ethylene polymer by the addition of aco-catalyst in an amount to effect a final ratio of equivalents ofaluminum to equivalents of chromium of from 0.1:1 to 10:1. In anotherembodiment, the step of contacting comprises contacting with diethylaluminum ethoxide. In another embodiment, the co-catalyst is selectedfrom the group consisting of triethyl aluminum, tri-isobutyl aluminum,and tri-n-hexyl aluminum. In another embodiment, the ratio ofequivalents of aluminum to equivalents of chromium is from about 1:1 toabout 3:1. In a preferred embodiment, the polymerization is gas phasepolymerization. In another embodiment, the catalyst is treated, incatalyst, with an alkyl aluminum or an alkyl aluminum alkoxide prior tothe addition of co-catalyst. In another specific embodiment, the alkylaluminum alkoxide is diethyl aluminum ethoxide and the ratio ofequivalents of aluminum to equivalents of chromium is between about 1:1and 10:1.

In another embodiment of the present invention there is a process forproducing an ethylene polymer comprising the steps of contactingethylene under polymerization conditions with a catalyst systemcomprising chromium oxide and a silica-containing support comprisingsilica selected from the group consisting of silica having (a) a porevolume of about 1.1-1.8 cm³/g and a surface area of about 245-375 m²/g,(b) a pore volume of about 2.4-3.7 cm³/g and a surface area of about410-620 m²/g, and (c) a pore volume of about 0.9-1.4 cm³/g and a surfacearea of about 390-590 m²/g; controlling catalyst activity, polymerM_(w)/M_(n), and polymer molecular weight of the resulting ethylenepolymer by the addition of a co-catalyst in an amount to effect a finalratio of equivalents of aluminum to equivalents of chromium of from0.1:1 to 10:1. In a preferred embodiment, the co-catalyst is selectedfrom the group consisting of triethyl aluminum, tri-isobutyl aluminum,and tri-n-hexyl aluminum. In a specific embodiment, the ratio ofequivalents of aluminum to equivalents of chromium is from about 1:1 toabout 3:1. In another embodiment, the polymerization is gas phasepolymerization.

Another embodiment of the present invention is a process for producingan ethylene polymer in a reactor comprising contacting ethylene underpolymerization conditions with a chrome catalyst system; conducting thepolymerization at a space-time-yield value of greater than 8; andoperating the polymerization at a catalyst productivity of greater than3000 kg polymer/kg catalyst and at a reaction temperature at least 2.5°C. higher than the reaction temperature when polymerizing with the samechrome catalyst system in the absence of triethyl aluminum and producingthe ethylene polymer at the same polymer molecular weight and densityusing the same space-time-yield value, ethylene partial pressure, H₂/C₂gas mole ratio and comonomer to C₂ gas mole ratio.

The foregoing has outlined rather broadly the features and technicaladvantages of the present invention in order that the detaileddescription of the invention that follows may be better understood.Additional features and advantages of the invention will be describedhereinafter which form the subject of the claims of the invention. Itshould be appreciated by those skilled in the art that the conceptionand specific embodiment disclosed may be readily utilized as a basis formodifying or designing other structures for carrying out the samepurposes of the present invention. It should also be realized by thoseskilled in the art that such equivalent constructions do not depart fromthe spirit and scope of the invention as set forth in the appendedclaims. The novel features which are believed to be characteristic ofthe invention, both as to its organization and method of operation,together with further objects and advantages will be better understoodfrom the following description when considered in connection with theaccompanying figures. It is to be expressly understood, however, thateach of the figures is provided for the purpose of illustration anddescription only and is not intended as a definition of the limits ofthe present invention.

BRIEF DESCRIPTION OF THE DRAWINGS

For a more complete understanding of the present invention, reference isnow made to the following descriptions taken in conjunction with theaccompanying drawing, in which:

FIG. 1. Possible structure of chromium oxide-on-silica (“Phillips”)catalyst.

FIG. 2. Possible structure of silylchromate-on-silica catalyst.

FIG. 3. Molecular weight plots of polyethylene produced with MS35100chromium oxide catalyst; (a) no DEALE; (b) In-situ DEALE; (c) DEALEadded to catalyst.

FIG. 4. Ethylene Flow versus Time for MS35100 chromium oxide catalyst.

FIG. 5. Molecular weight plots of polyethylene produced with 957HSchromium oxide catalyst; (a) no DEALE; (b) In-situ DEALE; (c) DEALEadded to catalyst.

FIG. 6. Ethylene Flow versus Time for 957HS chromium oxide catalyst.

FIG. 7. Molecular weight plots of polyethylene produced with EP352chromium oxide catalyst; (a) In-situ DEALE; (b) DEALE added to catalyst.

FIG. 8. Ethylene Flow versus Time for EP352 chromium oxide catalyst.

FIG. 9. Molecular weight plots of polyethylene produced withsilylchromate on MS3050 with DEALE added in-situ.

FIG. 10. Ethylene Flow versus Time for silylchromate on MS3050 silica.

FIG. 11. Molecular weight plots of polyethylene produced withsilylchromate on 955 silica; (a) no DEALE; (b) 5 eq DEALE/eq Cr;in-catalyst; (c) 10 eq DEALE/eq Cr; in-catalyst.

FIG. 12. Ethylene Flow versus Time for silylchromate on 955 silica.

FIG. 13. Activity versus Equivalents of Co-Catalyst (Al/Cr) for variousco-catalyst for silylchromate catalyst having 5 eq DEALE/eq Cr.

FIG. 14. Flow Index versus Equivalents of Co-Catalyst (Al/Cr) forvarious co-catalysts for silylchromate catalyst having 5 eq DEALE/eq Cr.

FIG. 15. Activity versus Time for silylchromate catalyst having 5 eqDEALE/eq Cr, with no co-catalyst; and in the presence of TEAL.

FIG. 16. Activity versus Time for silylchromate catalyst having 5 eqDEALE/eq Cr, with no co-catalyst; and in the presence of TIBA.

FIG. 17. Activity versus Time for silylchromate catalyst having 5 eqDEALE/eq Cr, with no co-catalyst; and in the presence of TNHAL.

FIG. 18. Molecular weight plot for silylchromate catalyst having 5 eqDEALE/eq Cr, produced polyethylene, no co-catalyst.

FIG. 19. Molecular weight plot for silylchromate catalyst having 5 eqDEALE/eq Cr, produced polyethylene, in the presence of TIBA.

FIG. 20. Molecular weight plot for silylchromate catalyst having 5 eqDEALE/eq Cr, produced polyethylene, in the presence of TEAL.

FIG. 21. Molecular weight plot for silylchromate catalyst having 5 eqDEALE/eq Cr, produced polyethylene, in the presence of TNHAL.

FIG. 22. Activity versus Time for silylchromate catalyst having 1.5 eqDEALE/eq Cr, with no co-catalyst; and in the presence of TEAL.

FIG. 23. Activity versus Time for silylchromate catalyst having 1.5 eqDEALE/eq Cr, with no co-catalyst; and in the presence of TNHAL.

FIG. 24. Activity versus Time for silylchromate catalyst having 1.5 eqDEALE/eq Cr, with no co-catalyst; and in the presence of TIBA.

FIG. 25. Molecular weight plot for silylchromate catalyst having 1.5 eqDEALE/eq Cr, produced polyethylene, no co-catalyst.

FIG. 26. Molecular weight plot for silylchromate catalyst having 1.5 eqDEALE/eq Cr, produced polyethylene, in the presence of TIBA.

FIG. 27. Molecular weight plot for silylchromate catalyst having 1.5 eqDEALE/eq Cr, produced polyethylene, in the presence of TEAL.

FIG. 28. Molecular weight plot for silylchromate catalyst having 1.5 eqDEALE/eq Cr, produced polyethylene, in the presence of TNHAL.

FIG. 29. Activity versus Equivalents of Co-Catalyst (Al/Cr) for variousco-catalysts for 957HS chromium oxide-TTIP catalyst having 5 eq DEALE/eqCr.

FIG. 30. Flow Index versus Equivalents of Co-Catalyst (Al/Cr) forvarious co-catalysts for 957HS chromium oxide-TTIP catalyst having 1.5eq DEALE/eq Cr.

FIG. 31. Molecular weight plot for 957HS chromium oxide-TTIPcatalyst-produced polyethylene, no co-catalyst.

FIG. 32. Molecular weight plot for 957HS chromium oxide-TTIPcatalyst-produced polyethylene, in the presence of TIBA.

FIG. 33. Molecular weight plot for 957HS chromium oxide-TTIPcatalyst-produced polyethylene, in the presence of TEAL.

FIG. 34. Molecular weight plot for 957HS chromium oxide-TTIPcatalyst-produced polyethylene, in the presence of TNHAL.

FIG. 35. Molecular weight plot for 957HS chromium oxide-TTIPcatalyst-produced polyethylene, no co-catalyst.

FIG. 36. Molecular weight plot for 957HS chromium oxide-TTIPcatalyst-produced polyethylene, in the presence of TEB.

DETAILED DESCRIPTION OF THE INVENTION

The invention is applicable to the polymerization of olefins by anysuspension, solution, slurry, or gas phase process, using knownequipment and reaction conditions, and is not limited to any specifictype of polymerization system. Generally, olefin polymerizationtemperatures range from about 0° C. to about 300° C. at atmospheric,subatmospheric, or superatmospheric pressures. Slurry or solutionpolymerization systems may utilize subatmospheric or superatmosphericpressures and temperatures in the range of about 40° C. to about 300° C.A useful liquid phase polymerization system is described in U.S. Pat.No. 3,324,095. Liquid phase polymerization systems generally comprise areactor to which olefin monomer and catalyst composition are added, andwhich contains a liquid reaction medium for dissolving or suspending thepolyolefin. The liquid reaction medium may consist of the bulk liquidmonomer or an inert liquid hydrocarbon that is nonreactive under thepolymerization conditions employed. Although such an inert liquidhydrocarbon need not function as a solvent for the catalyst compositionor the polymer obtained by the process, it usually serves as solvent forthe monomers employed in the polymerization. Among the inert liquidhydrocarbons suitable for this purpose are isopentane, hexane,cyclohexane, heptane, benzene, toluene, and the like. Reactive contactbetween the olefin monomer and the catalyst composition should bemaintained by constant stirring or agitation. The reaction mediumcontaining the olefin polymer product and unreacted olefin monomer iswithdrawn from the reactor continuously. The olefin polymer product isseparated, and the unreacted olefin monomer and liquid reaction mediumare recycled into the reactor.

The invention is, however, especially useful with gas phasepolymerization systems, with superatmospheric pressures in the range of1 to 1000 psi, preferably 50 to 400 psi, most preferably 100 to 300 psi,and temperatures in the range of 30 to 130° C., preferably 65 to 110° C.Stirred or fluidized bed gas phase polymerization systems areparticularly useful. Generally, a conventional gas phase, fluidized bedprocess is conducted by passing a stream containing one or more olefinmonomers continuously through a fluidized bed reactor under reactionconditions and in the presence of catalyst composition at a velocitysufficient to maintain a bed of solid particles in a suspendedcondition. A stream containing unreacted monomer is withdrawn from thereactor continuously, compressed, cooled, optionally partially or fullycondensed, and recycled into the reactor. Product is withdrawn from thereactor and make-up monomer is added to the recycle stream. As desiredfor temperature control of the polymerization system, any gas inert tothe catalyst composition and reactants may also be present in the gasstream. In addition, a fluidization aid such as carbon black, silica,clay, or talc may be used, as disclosed in U.S. Pat. No. 4,994,534.

The polymerization system may comprise a single reactor or two or morereactors in series, and is conducted substantially in the absence ofcatalyst poisons. Organometallic compounds may be employed as scavengingagents for poisons to increase the catalyst activity. Examples ofscavenging agents are metal alkyls, preferably aluminum alkyls.

Conventional adjuvants may be used in the process, provided they do notinterfere with the operation of the catalyst composition in forming thedesired polyolefin. Hydrogen may be used as a chain transfer agent inthe process, in amounts up to about 10 moles of hydrogen per mole oftotal monomer feed.

Polyolefins that may be produced according to the invention include, butare not limited to, those made from olefin monomers such as ethylene andlinear or branched higher alpha-olefin monomers containing 3 to about 20carbon atoms. Homopolymers or interpolymers of ethylene and such higheralpha-olefin monomers, with densities ranging from about 0.86 to about0.95 may be made. Suitable higher alpha-olefin monomers include, forexample, propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene,1-octene, and 3,5,5-trimethyl-1-hexene. Olefin polymers according to theinvention may also be based on or contain conjugated or non-conjugateddienes, such as linear, branched, or cyclic hydrocarbon dienes havingfrom about 4 to about 20, preferably 4 to 12, carbon atoms. Preferreddienes include 1,4-pentadiene, 1,5-hexadiene, 5-vinyl-2-norbomene,1,7-octadiene, vinyl cyclohexene, dicyclopentadiene, butadiene,isobutylene, isoprene, ethylidene norbomene and the like. Aromaticcompounds having vinyl unsaturation such as styrene and substitutedstyrenes, and polar vinyl monomers such as acrylonitrile, maleic acidesters, vinyl acetate, acrylate esters, methacrylate esters, vinyltrialkyl silanes and the like may be polymerized according to theinvention as well. Specific polyolefins that may be made according tothe invention include, for example, high density polyethylene, mediumdensity polyethylene (including ethylene-butene copolymers andethylene-hexene copolymers) homo-polyethylene, polypropylene,ethylene/propylene rubbers (EPR's), ethylene/propylene/diene terpolymers(EPDM's), polybutadiene, polyisoprene and the like.

Reduced chromium oxide-on-silica catalysts represent one pathway toimproved catalyst systems for polyethylenes having characteristics ofthose typically formed using silylchromate-on-silica catalysts. It isdesired that any such catalytic system perform well during highspace-time yield operation (i.e., operation maximizing polymer producedper unit reactor time and reactor space), producing the greatest amountof polyethylene possible with high catalyst activity in a shorterresidence time. Chromium oxide catalysts possess adequate productivityand activity, yet polyethylenes produced through their use are less thanoptimal for a number of applications where high molecular weight, broadmolecular weight distribution, and the presence of some degree ofbimodality of molecular weight distribution are desired.

The so-called Phillips catalyst, introduced in the early 1960s was thefirst chromium oxide-on-silica catalyst. The catalyst is formed byimpregnating a Cr⁺³ species into silica, followed by fluidization of thesilica matrix at ca. 400° C.-860° C. Under these conditions, Cr⁺³ isconverted to Cr⁺⁶. The Phillips catalyst is also commonly referred to inthe prior art as “inorganic oxide-supported Cr⁺⁶.” While chromiumoxide-on-silica catalysts exhibit good productivity, they producepoylethylenes having relatively narrow molecular weight distribution.The so-called Phillips catalyst and related catalysts are hereinreferred to as “CrOx” catalysts. FIG. 1 gives a schematic representationof the structure of CrOx catalysts. Silylchromate-on-silica catalystsare one type of inorganic oxide-supported Cr⁺⁶ catalyst that producespolyethylenes not having the aforementioned deficiencies.Silylchromate-on-silica catalysts are referred to herein as “SC”catalysts. FIG. 2 gives a schematic representation of the structure ofSC-type catalysts. SC-type catalysts are typically reduced with aluminumalkyls, such as DEALE, during a catalyst preparation step prior toaddition to the reactor. It is and has been a goal to preserve orimprove productivity of CrOx catalysts, while producing a polyethylenewith molecular weight and molecular weight distributions more closelyapproaching those produced with SC catalysts.

Variations on catalysts employing Cr⁺⁶ species supported on silica havebeen known. One particular variation uses titanium tetraisopropoxide(TTIP) impregnated onto silica along with the Cr⁺³ species beforeactivation. This variation is hereinafter referred to as “Ti—CrOx”(titanated chromium oxide). Such modifications result in polyethyleneswith slightly greater molecular weight distributions compared to thosemade without titanation. While this system produces polyethylenestending towards those produced using silylchromate-on-silica typecatalysts, further improvements in molecular weight and molecular weightdistribution more closely approaching those obtained withsilylchromate-on-silica are desired.

EXAMPLES

Examples 1 through 53 were conducted as slurry polymerization reactions.Examples 54 through 74 were conducted in a gas phase fluid bed reactor.

General Catalyst Preparations

Unless otherwise noted the catalysts used in the following examples wereall made by the following procedures.

General Preparation A. Chromium oxide catalyst activation: Catalysts wasreceived from the suppliers with the chromium already impregnated on thesupports. The catalyst physical properties are described in Table 2.Activation is conducted by passing gas through the catalyst for fourhours at the specified temperature in dry air. This is usually conductedin a tube furnace. The catalyst is then stored under nitrogen untilused.

General Preparation B. Chromium oxide catalyst reductions: In a typicalpreparation 3 grams of previously activated catalyst is placed in a 50mL airless ware flask with a stir bar under inert atmosphere.Thirty-five mL of dry degassed hexane is added and the mixture is heatedto 50° C. The reducing agent is then added via syringe (all reagents are20-25 wt % in hexane). The stated equivalents are always the ratio ofreagent to chromium. After 30 minutes, drying is commenced. This can bedone under high vacuum or with a nitrogen purge. Catalyst is storedunder nitrogen until used.

General Preparation C. SC-type Catalyst Preparations All silicas aredehydrated prior to use. Silica dehydration is conducted by passing gasthrough the catalyst for four hours at the specified temperature in dryair or nitrogen. In a typical preparation 3 grams of previouslydehydrated silica is placed in a 50 mL airless ware flask with a stirbar under inert atmosphere. Thirty-five mL of dry degassed hexane isadded and the mixture is heated to 50 C. The organochrome source(triphenyl silylchromate (TPSC)) can be added prior to, at the same timeas, or after addition of the diluent. The mixture is typically stirredfor 2 hours (where stated, stirring can continue for 10 hours). Thereducing agent is then added via syringe (all reagents are 20-25 wt % inhexane). The stated equivalents are always the ratio of reagent tochromium. After 30 minutes, drying is commenced. This can be done underhigh vacuum or with a nitrogen purge. Catalyst is stored under nitrogenuntil used. In cases where no reducing agent is added, drying commencesafter the chrome source and silica have been mixed as above.

Catalyst Descriptions

When used, the ratio of reducing agent to chromium added can be found inthe example; “in reactor” means the reagent was added separately fromthe catalyst. “In catalyst” means the reagent is added in a catalystpreparation step. Recited wt % values for chromium are approximate;actual values can range±50%. This applies for both chromium oxide andsilylchromate catalysts.

Example 1

The catalyst was used as supplied by Davison Chemical and consists of0.5 wt % chromium on Davison 955 silica and was activated at 825C(General preparation A). See silica specifications in Table 2.

Examples 2-6

The catalyst is the same as that used in Example 1 except that reducingagents are added in a catalyst preparation step as in Generalpreparation B. When a mixture of reducing agents are used the moleratios of each is 1:1.

Example 7

The catalyst consists of 0.5 wt % Cr on Davison 955 silica (200° C.dehydration) treated with titanium tetraisopropoxide prior toactivation. Enough TTIP is added so after activation 3.8 wt % Ti remains(see U.S. Pat. No. 4,011,382 for specific procedures for TTIP addition).

Examples 8-9

The catalyst is the same as that used in Example 7 except that areducing agent is added in a catalyst preparation step as in Generalpreparation B.

Examples 10-12

MS35100 is a chromium oxide catalyst obtained from PQ with thespecifications listed in Table 2. The catalyst contains 0.5 wt % Cr. Thecatalyst is activated at 700° C. (General preparation A). When used,reducing agent is added in a catalyst preparation step as in Generalpreparation B.

Examples 13-15

The catalyst is the same as that used in Example 1 with the addition ofDEALE as a reducing agent using General preparation B.

Examples 16-18

EP352 is a chromium oxide catalyst obtained from Ineos with thespecifications listed in Table 2. The catalyst contains 0.5 wt % Cr. Thecatalyst is activated at 700° C. (General preparation A). When used,reducing agent is added in a catalyst preparation step as in Generalpreparation B.

Examples 19-21

Triphenysilylchromate is added to MS3050 support (which has beenpreviously dehydrated at 700° C.) as in General preparation C. Enoughtriphenyl silylchromate is added so the final dried composition contains0.5 wt % Cr. When used, reducing agent is added in a catalystpreparation step as in General preparation C.

Examples 22-25 and 27

Triphenysilylchromate is added to Davison 955 support (which has beenpreviously dehydrated at 600° C.) as in General preparation C. Enoughtriphenyl silylchromate is added so the final dried composition contains0.24-0.25 wt % Cr. When used, DEALE reducing agent is added in acatalyst preparation step as in General preparation C.

Example 26

Triphenysilylchromate is added to Davison 955 support (which has beenpreviously dehydrated at 600° C.) as in General preparation C. Enoughtriphenyl silylchromate is added so the final dried composition contains0.25 wt % Cr. Tri-isobutylaluminum reducing agent is added in a catalystpreparation step as in General preparation C.

Examples 28-34

This catalyst was produced on a commercial scale. Triphenysilylchromateis added to Davison 955 support (which has been previously dehydrated at600° C.) as in General preparation C. Enough triphenyl silylchromate isadded so the final dried composition contains 0.24 wt % Cr. The TPSC isallowed to mix with the silica for 10 hours before the addition ofDEALE. A 5:1 ratio of DEALE/Cr was used.

Examples 35-38

The same catalyst as that used in Example 28 was used here except thatthe ration of DEALE/Cr was 1.5.

Examples 39-45, 50-53

The same catalyst as that used in example 7 was used here. Co-catalystslisted under addition were added separately to the reactor.

Examples 46-49 and 74

The same catalyst as that used in example 1 was used here. Co-catalystlisted under addition is added separately to the reactor.

Examples 54, 55, 60-68 and 72

This catalyst was produced on a commercial scale (with the exception of55, which was prepared on lab pilot plant scale).

Triphenysilylchromate is added to Davison 955 support (which has beenpreviously dehydrated at 600° C.) as in General preparation C. Enoughtriphenyl silylchromate is added so the final dried composition contains0.24 wt % Cr. The TPSC is allowed to mix with the silica for 10 hoursbefore the addition of DEALE. A 5:1 ratio of DEALE/Cr was used.Co-catalysts listed as added to the reactor were added separately to thereactor.

Examples 69, 70, 71,74

This catalyst was produced on a commercial scale.Bis-triphenysilylchromate is added to Davison 955 support (which hasbeen previously dehydrated at 600° C.) as in General preparation C.Enough triphenyl silylchromate is added so the final dried compositioncontains 0.25 wt % Cr. The TPSC is allowed to mix with the silica for 10hours before the addition of DEALE. A 1.5:1 ratio of DEALE/Cr was used.Co-catalysts listed as added to the reactor were added separately to thereactor.

Example 56

This catalyst is the same as that used in Example 19 but was prepared ona pilot plant scale. A 5:1 ratio of DEALE/Cr was used.

Examples 57 and 58

The catalyst is the same as that used in Example 13 employing DEALE asthe reducing agent at a 5:1 DEALE/Cr ratio and was prepared on a pilotplant scale.

Example 59

The catalyst is the same as that used in Example 10 employing DEALE asthe reducing agent at a 5:1 DEALE/Cr ratio and was prepared on a pilotplant scale.

Although the specific examples describe specific loadings ofsilylchromate onto silica supports, it should be understood thatloadings of about 0.2-1.0 weight % of chromium are useful and part ofthe instant invention.

Lab Slurry Procedure

A one liter stirred reactor was used for the polymerization reactions.The reactor was thoroughly dried under a purge of nitrogen at elevatedtemperatures before each run. 500 mL of dry degassed hexane was fed tothe reactor at 60° C. If used, hexene is added at this point. Unlessotherwise noted 10 mL of 1-hexene is used in each experiment. A smallquantity (0.1-0.25 g) of Davison 955 silica dehydrated at 600° C. andtreated with 0.6 mmole/g of TEAL is then added to the reactor topassivate any impurities. No TEAL treated silica was added in any runwhere a reagent was added to the reactor separately from the catalyst.After stirring for 15 minutes the catalyst is charged followed byadditional reagents. Co-catalysts are added directly to the reactor asdiluted solutions as mention elsewhere. The reactor is sealed andhydrogen is charged at this point. Hydrogen is only used where noted inthe tables. The reactor is charged to 200 psi with ethylene. Ethylene isallowed to flow to maintain the reactor pressure at 200 psi. Ethyleneuptake is measure with an electronic flow meter. All copolymerizationswere run at 85° C.; homopolymerizations were run at 90° C.Polymerizations were run until a maximum of 160 grams PE were made orterminated sooner. The reactor was opened after depressurization and thetemperature lowered. The polymer weight was determined after allowingthe diluent to evaporate. The polymer was then characterized employing anumber of tests.

Tests

Density: ASTM D-1505.

Melt Index: (I₂) ASTM D-2338 Condition E measured at 190° C. reported asgrams per 10 minutes.

Flow Index: (I₂₁) ASTM D-1238 Condition F measured 10 times the weightas used in Melt Index above.

MFR: Melt Flow ratio is the Flow index/Melt index.

SEC: Polymer Laboratories instrument; Model: HT-GPC-220, Columns:Shodex, Run Temp: 140° C., Calibration Standard: traceable to NIST,Solvent: 1,2,4-Trichlorobenzene.

BBF: Butyl branching frequency as measured by ¹³C-NMR. The value is thenumber of butyl branches per 1000 carbon atoms.

The inventors have found that systems employing reduced chromium oxidecatalysts on silica exhibit the desired productivity while producingpolyethylenes having molecular weight and molecular weight distributionsimilar to those obtained with silylchromate-on-silica. The addition ofalkyl aluminum compounds such as triethylaluminum (TEAL), either 1)directly to the catalyst prior to introduction into the reaction or 2)added directly to the reactor (in-situ) increases the molecular weightand molecular weight distribution of the resulting polyethylenes. Ingeneral, the alkyl groups of the trialkylaluminum can be the same ordifferent, and should have from about 1 to about 12 carbon atoms andpreferably 2 to 4 carbon atoms. Examples include, but are not limitedto, triethylaluminum, tri-isopropylaluminum, tri-isobutyl aluminum,tri-n-hexyl aluminum, methyl diethylaluminum, and trimethylaluminum.Although the examples almost exclusively use TEAL, it should beunderstood that the invention is not so limited. However, TEAL resultsin some uncontrolled side branching in the polymer. It would bebeneficial to eliminate this side branching in applications where it isnot desired, yet preserve it for applications where it is desired. Thiscan be achieved by the addition of alkyl aluminum alkoxide compoundssuch as diethyl aluminum ethoxide. Use of an alkyl aluminum alkoxidesuch as diethylaluminum ethoxide (DEALE) eliminates the side branching.In general, the alkyl aluminum alkoxide, having the general formulaR₂—Al—OR where the alkyl groups may be the same or different, shouldhave from about 1 to about 12 carbon atoms and preferably 2 to 4 carbonatoms. Examples include but are not limited to, diethyl aluminumethoxide, diethyl aluminum methoxide, dimethyl aluminum ethoxide,di-isopropyl aluminum ethoxide, diethyl aluminum propoxide, di-isobutylaluminum ethoxide, and methyl ethyl aluminum ethoxide. Although theexamples almost exclusively use DEALE, it should be understood that theinvention is not so limited. The data of Table 1 illustrates thereaction conditions and the characteristics of the resulting polymerwhen TEAL and DEALE are used with CrOx catalysts (chromiumoxide-on-silica). The numerical prefixes listed before the aluminumalkyl in each case represents the mole ratio of aluminum to chromium. InTable 1, CrOx catalyst is produced by impregnating chromium oxide onGrace 955 silica, followed by air fluidization and heating to about 825°C. Ti—CrOx catalyst is produced in a similar fashion with the exceptionthat titanium tetraisopropoxide is also added to the silica prior tofluidization and activation. The reducing agents are added as anadditional catalyst preparation step.

TABLE 1 Effect of TEAL and DEALE on chromium catalyst performance. BulkExample 1- Time YIELD Flow Act.gPE/g Density No. Catalyst treatmentHexene (min) (g) Index cat-1 hr (g/cc) BBF Den. g/cc CrOx on 955 silica1 none 10 51 157 5.5 1,816 0.37 3.8 0.9415 2 5 eq. TEAL 10 46 116 1.91,328 0.29 2.6 0.9434 3 5 eq. TEAL 0 65 115 6.8 911 0.22 2.4/1.0 0.94384 5 eq. DEALE 10 46 147 22.3 1,631 0.32 0.8 0.9573 5 5 eq. TEAL/DEALE 1054 146 7.5 1,680 0.30 1.2 0.9531 6 5 eq. TEAL/DEALE 0 34 124 4.1 2,3660.26 non det 0.9586 Ti—CrOx on 955 silica 7 none 10 65 163 6.9 1,8860.32 3.0 0.9433 8 5 eq. TEAL 10 77 151 2.1 1,096 0.29 2.7 0.9455 9 5 eq.TEAL 0 70 136 3.0 941 0.28 0.5/0.5 0.9531

CrOx Catalyst

Referring to the examples in Table 1, Example 1 reveals that under thepolymerization conditions described, 3.8 butyl branches per 1000 carbonatoms are observed by NMR analysis. This shows the extent of comonomerincorporation into the polymer. Example 2 shows that when the catalystis treated with TEAL the amount of hexene incorporated drops slightlyunder the same conditions; while polymer flow index is lowered. Example3 demonstrates that significant branching is found when the catalyst istreated with TEAL even though no comonomer is present. In this case bothbutyl (2.4) and ethyl branches (1.0) are detected. When the catalyst istreated with DEALE lower polymer side chains are detected indicatinglower comonomer incorporation has occurred (Example 4). When thecatalyst reducing agent is a combination of TEAL and DEALE it can beseen that the comonomer incorporation rate is between that found witheither reducing agent alone (Example 5). When this combination ofcatalyst reducing agents are used to make catalyst and the catalyst runin a homopolymerization reaction it can be seen in Example 6 that sidechains are not detected. This shows that DEALE is suppressing formationof side chain branches in the absence of comonomer. Both in the presenceand absence of hexene, the addition of DEALE significantly decreases andsometimes eliminates side chain branching in the resulting ethylenepolymer.

Making comparisons using productivity (g polyethylene/g catalyst) oractivity (g polyethylene/g catalyst-hour), the presence of hexenebecomes beneficial, improving productivity and activity. The trends inmolecular weight of the produced polymers can be gleaned from a reviewof the Flow Index (FI) results. Comparing FI values for polymer producedwith CrOx catalyst in the absence of TEAL to those produced in thepresence of TEAL reveals an increase in molecular weight as indicated bythe decrease in flow index. Thus, judicious application of TEAL andDEALE during catalyst preparation affords the ability to modifymolecular weight and molecular weight distribution and simultaneouslycontrol side chain branching in these chromium oxide-based catalysts.This technology will be useful in making higher density polymers.

In summary, addition of DEALE decreases branching and increasesmolecular weight for CrOx produced polymers. Addition of TEAL increasesmolecular weight of the produced polymer and increases the generation ofside chain branches when comonomer is not present.

Ti—CrOx Catalyst

Ti—CrOx catalyst is the same as CrOx with the exception that titanium 5tetraisopropoxide is co-impregnated with the chromium oxide onto thesilica before activation (Examples 7-9 on Table 1). The same molecularweight trend seen for CrOx catalyst is observed for Ti—CrOx catalyst inthe presence of TEAL compared with no reducing agent.

Effect of DEALE Addition

It has also been found that the productivity of chromium-based catalystscan be increased by adding an activator such as DEALE directly to thereactor or as part of the catalyst preparation step. Consistent with thediscussion above, control of polymer molecular weight and molecularweight distribution is another feature of the invention.

Chromium oxide-based catalysts have high activity with moderateinduction times. These catalysts produce polymers with intermediatemolecular weight distribution. Addition of reagents such as DEALE to thepolymerization reactor with these catalysts eliminates the inductionperiod and increases activity (boosting productivity). The presence ofDEALE also modifies the molecular weight distribution. Productivity isparticularly poor in the case of silychromate-on-silica-type catalysts(SC) in the absence of reducing agents due to long induction times. Ithas been found that in-situ addition of DEALE effectively eliminatesinduction times in silychromate-on-silica-type catalyst systems.

Table 2 lists several exemplary commercial silica supports with theirphysical properties. The effect of the presence of DEALE and of thereduction method employed (direct addition to catalyst prior topolymerization versus direct addition (in-situ) to the reactor) wasstudied. These silica support are illustrative examples and notexhaustive of the types of silica which may be used in the presentinvention. Other silica supports commonly used in the filed and known tothose of skill in the art are also useful herein. Table 2 providesapproximate pore volume, surface area, average pore diameter, averagepore size and percent titanium for the silica supports used in thisstudy. The label is that used by the supplier to describe the support.The number without the parentheses is the name of the support suppliedas silica alone. The number in parentheses is the name of the supportwhen it is supplied with a chromium salt already impregnated on thesupport. Although these silcas were obtained from the suppliers anysilica fitting the specifications below would be expected to function ina similar manner. The present invention is not limited to any specificcommercial silica support but may be used with any silicas having a porevolume of about 1.1 to about1.8 cm³/g and a surface area of about245-375 m²/g; or a pore volume of about 2.4 to about3.7 cm³/g and asurface area of about 410-620 m²/g; or a pore volume of about 0.9 toabout1.4 cm³/g and a surface area of about 390-590 m²/g.

TABLE 2 Commercial Silica Supports and Physical Properties Pore SurfaceAverage Silica Volume Area Pore Average Pore Support (cm³/g) (m²/g)Diameter (Å) Size (μm) Ti (%) Grace 955 1.45 310 210 55 — (957) PQMS3050 3.02 513 198 90 — (35100) Ineos EP52 1.15 490 90 70 2.60 (352)

MS 35100 CrOx catalyst (chromium oxide-on-silica) was studied forperformance 1) in the absence of DEALE, 2) when DEALE was added directlyto the catalyst and 3) when it was added to the reactor in situ.Reactions were performed in 500 mL of hexane slurry with 10 mL of1-hexene added; the reaction was run at 85° C. and 200 psi totalpressure. FIG. 3 illustrates the molecular weight distribution of theresulting polymer in the absence and presence of DEALE. In the absenceof DEALE (FIG. 3( a)), the resulting polymer has a molecular weightdistribution of 16.9. When DEALE is added in-situ (FIG. 3( b)), abroadening of the molecular weight is observed, with a shoulder becomingapparent at a molecular weight distribution of 23.8. Similar but lesspronounced results occur when DEALE is added to the catalyst beforepolymerization (FIG. 3( c)), the high molecular weight shoulder beingslightly less prominent. When DEALE is added directly to the catalyst, apolymer molecular weight distribution of 32.4 is recovered. A similartrend is observed in the value of M_(Z)/M_(W) as DEALE is added.M_(Z)/M_(W) is indicative of the high molecular weight shoulder; asM_(Z)/M_(W) increases, the desirable high molecular weight shoulderbecomes more pronounced. M_(Z)/M_(W) data are obtained from SEC analysisof the polymer. In the absence of DEALE (FIG. 3( a)), a value ofM_(Z)/M_(W) of 5.7 is recovered. When DEALE is added in-situ and to thecatalyst (FIGS. 3( b) and 3(c)), one recovers M_(Z)/M_(W) values ofabout 7.7 and 9.6, respectively.

Increases in polymer density and activity of catalyst are realized bothin the direct addition to catalysts (in catalyst) and in the in-situaddition (in reactor) as evidenced in Table 3. Comonomer incorporation,as evidenced by the branching parameter (BBF) indicates a decrease incomonomer incorporation rate for both in-situ added DEALE and DEALEadded to catalyst, in comparison with the absence of DEALE. There is amodest molecular weight decrease, as evidenced by an increase in flowindex upon the use of DEALE. As demonstrated in FIG. 4, induction timesare virtually eliminated when DEALE is added, either in-situ or directlyto the catalyst prior to polymerization. The elimination of inductiontimes for DEALE addition in-situ or to catalyst contrast with the longinduction times observed for the same catalyst system in the absence ofDEALE. In conclusion, in-situ addition of DEALE behaves comparably toDEALE added to the catalyst prior to polymerization for this CrOxcatalyst.

TABLE 3 Effect of DEALE of MS35100 CrOx catalyst Bulk Example Time YIELDFlow Act.gPE/ Density Mn Mw Mz Den. No. DEALE (min) (g) Index gcat-1 hr(g/cc) (× 10³) (× 10³) (× 10⁶) Mw/Mn Mz/Mw BBF g/cc 10 none 52 123 2.8974 0.31 17.9 304 1.74 16.9 5.7 5.1 0.9372 11 5 eq. in reactor 93 1606.9 1,272 0.30 11.2 267 2.06 23.8 7.7 1.6 0.9533 12 5 eq. in catalyst 60163 18.5 1,457 0.36 6.4 208 1.99 32.4 9.6 1.7 0.9562

The same experiments were performed with 957HS chromium oxide catalysts.Reactions were performed in 500 mL of hexane slurry with 10 mL of1-hexene added; the reaction was run at 85° C. and 200 psi totalpressure. FIG. 5 illustrates the molecular weight distribution of theresulting polymer in the absence and presence of DEALE. In the absenceof DEALE (FIG. 5( a)), the resulting polymer exhibits a molecular weightdistribution of 9.7 and a molecular weight of well under 500,000. WhenDEALE is added in-situ (FIG. 5( b)), an increase of the polymermolecular weight distribution is observed to a value of about 12.0.M_(Z)/M_(W) values demonstrate that a high molecular weight shoulderappears upon the addition of DEALE, M_(Z)/M_(W) being about 4.5 in theabsence of DEALE and about 8.6 and about 8.3, respectively for DEALEadded in-situ and DEALE added to the catalyst. Increases in density anddecreased side-chain branching are realized for both the direct additionto catalysts and for the in-situ addition (in reactor) as evidenced inTable 4. A moderate decrease in molecular weight is demonstrated by theincrease in flow index. Similar to the effect observed for MS35100 CrOxcatalyst, the addition of DEALE to 957HS CrOx catalyst, either throughin-situ addition or direct addition to catalyst results in a virtualelimination of induction time, thereby improving activity of thecatalyst (FIG. 6). In conclusion, addition of DEALE in-situ to this CrOxcatalyst system results in higher activity, lower molecular weight,comparable molecular weight distribution, and with comparable comonomerincorporation as the case where DEALE is added directly to the catalystprior to polymerization. Both the in-situ addition and the directaddition to polymer yields essentially zero induction time relative tothe finite induction times observed in the absence of DEALE.

TABLE 4 Effect of DEALE on 957HS CrOx Catalyst Bulk Time YIELD FlowAct.gPE/ Density Mn Mw Mz Mz/ Den. EX. NO. DEALE (min) (g) Index gcat-1hr (g/cc) (× 10³) (× 10³) (× 10⁶) Mw/Mn Mw BBF g/cc 13 none 58 153 2.61,429 0.34 25.1 243 1.09 9.68 4.47 3.7 0.9392 14 5 eq. in reactor 33 17215.1 2,978 0.31 15.7 189 1.62 12.03 8.60 1.1 0.9553 15 5 eq. on catalyst85 159 7.5 1,387 0.34 10.3 239 1.99 23.13 8.32 0.6 0.9574

EP352 CrOx catalyst was also studied for performance 1) in the absenceof DEALE, 2) when DEALE was added directly to the catalyst and 3) whenit was added to the reactor in situ. Reactions were performed in 500 mLof hexane slurry with 10 mL of 1-hexene added; the reaction was run at85° C. and 200 psi total pressure. FIG. 7 illustrates the molecularweight distribution of the resulting polymer in the presence of DEALE.When DEALE is added in-situ (FIG. 7( a)), a broader molecular weightdistribution is observed in comparison to DEALE added directly to thecatalyst (FIG. 7(b)) with the presence of a high molecular weightshoulder in both cases, similar to that observed for EP352 CrOx catalystwith no DEALE. Increases in polymer density and lower side-chainbranching are realized both in the direct addition to catalysts (incatalyst) and in the in-situ addition (in reactor) as evidenced in Table5. However, addition of DEALE in-situ to EP352 CrOx catalyst results inlittle change in activity relative to the that observed in the absenceof DEALE. This is in stark contrast to the addition of DEALE directly tothe catalyst prior to polymerization, where a substantial improvement incatalyst activity is observed. FIG. 8 demonstrates the improvement ininduction time in the presence of DEALE; the improvement being realizedboth when the DEALE is added in-situ and when it is added to thecatalyst. In conclusion, addition of DEALE in-situ to this CrOx catalystsystem results in higher activity, broader molecular weight distributionand comparable comonomer incorporation to that observed when DEALE isadded directly to the catalyst prior to polymerization. Induction timeis improved with either method of DEALE addition in comparison to theabsence of DEALE.

TABLE 5 Effect of DEALE on EP352 CrOx Catalyst Bulk Ex. Time YIELD FlowAct.gPE/ Density Mn × No. DEALE (min) (g) Index gcat-1 hr (g/cc) 10³ Mw× 10³ Mz × 10⁶ Mw/Mn Mz/Mw BBF Den. g/cc 16 none 67 160 4.7 2,014 0.3313.3 263 1.48 19.84 5.63 2.7 0.9425 17 5 eq. in reactor 60 155 4.1 1,8240.26 12.9 273 1.83 21.22 6.70 1.4 0.9529 18 5 eq. in catalyst 32 160 3.22,329 0.27 11.7 209 1.42 17.88 6.76 1.0 0.9548

Similar data for SC catalyst on MS3050 is illustrated in FIGS. 9 and 10and Table 6. As can be seen from FIG. 10, addition of DEALE effects astark improvement in induction time; virtually eliminating inductiontime for SC catalyst. This is also seen in the significant improvementis activity as shown in Table 6. Long induction times are the majorweakness of silylchromate-on-silica catalysts, in-situ addition of DEALEor other alkyl aluminum compounds significantly increases activitythrough elimination of induction time. The molecular weight of theproduced polymer is lowered as evidenced by a significant increase inflow index. While the molecular weight of the resulting polymer isdecreased, this has enhanced applicability in a two-catalyst system,with the use of an additional catalyst to produce high molecular weightpolymer.

TABLE 6 Effect of DEALE on SC Catalyst on MS3050. Bulk Example TimeYIELD Flow Act.gPE/ Density No. DEALE (min) (g) Index gcat-1 hr (g/cc)BBF Den. g/cc 19 none 227 152 3.8 111 0.44 1.7 0.9545 20 5 eq. inreactor 67 158 49.1 1,157 0.31 1.5 0.9603 21 5 eq. in catalyst 50 154112.5 724 0.42 1.4 0.9592

SC catalyst on Grace 955 silica was also studied. Again, a markedimprovement in induction time is observed when DEALE is added. This isimportant, as long induction time is a major disadvantage when usingsilylchromate-on-silica type catalysts. As shown in FIG. 11, themolecular weight and molecular weight distribution behavior is notsignificantly altered by the in-catalyst addition of DEALE to this SCcatalyst. From the data in Table 7, one can see that this is not thecase when DEALE is added in-situ. In all cases, the addition of DEALEvirtually eliminates induction time (FIG. 12). In-situ additionsignificantly increases activity and lowers polymer molecular weight.Use of TIBA with SC-type catalysts provides a catalyst system that hashigh productivity and makes polymer with higher molecular weight thanthat found when DEALE is used as the reducing agent. This is especiallyimportant to maintain polymer molecular weight at shorter residencetimes. Other alkyaluminum compounds, such as triethylaluminum andtri-n-hexylaluminum, would be expected to work in a similar manner.

TABLE 7 Effect of DEALE on SC Catalyst on 955 Silica. Bulk Example TimeYIELD Flow Act.gPE/ Density Mn Mw Mz No. DEALE (min) (g) Index gcat-1 hr(g/cc) (× 10³) (× 10³) (× 10⁶) Mw/Mn Mz/Mw Den. g/cc 22 none 162 12711.4 129 0.33 7.8 209 1.68 26.7 8.0 0.9505 23 5 eq. in reactor 100 10173.6 267 0.36 7.8 134 1.27 17.2 9.5 0.9636 24 5 eq. in catalyst 118 1565.2 319 0.46 11.0 233 1.49 21.1 6.4 0.9516 25 10 eq. in catalyst 100 16044.6 809 0.35 6.3 167 1.88 26.3 11.3 0.9612 26 5 eq. TIBA in 56 1559.57* 572 0.36 8.0 257 1.96 32.3 7.6 0.9531 catalyst 27 5 eq. DEALE in48 158 35.48* 526 0.45 0.9566 catalyst *run with 500 cc H₂ present

In summary, the use of DEALE or TIBA with silylchromate catalystsresults in polymer molecular weight characteristics (molecular weight,molecular weight distribution, high molecular weight shoulders, etc.)similar to those obtained without the use of DEALE or TIBA, but withbetter productivities than in the absence of these aluminum compounds.Thus, the positive molecular weight attributes of silylchromate-producedpolymers are preserved with the use of DEALE or TIBA with a concomitantincrease in activity. Use of TEAL and DEALE with CrOx catalysts resultsin polymers more similar to those produced with SC catalysts, whilepreserving the desirable activities inherent in CrOx polymers.Continuously varying the TEAL and DEALE in both CrOx and SC catalystsystems allows a mechanism to tailor the characteristics of thepolyethylene so produced while preserving good activities. In this way,the space time yield (weight of polymer per unit of reactor volume perunit of time) can be optimized for a number of different polyethylenegrades.

Effect of Co-Catalyst on Performance

The effect of co-catalyst on the performance of SC catalyst (treatedwith 5 equivalents of DEALE/Cr) was studied using the followingco-catalysts: TEAL, TIBA (tri-isobutyl aluminum), and TNHAL (tri-n-hexylaluminum). Although examples are limited to specific co-catalysts, itshould be understood that other alkyl aluminum compounds are applicableand are a part of the invention herein. Table 8 and FIG. 13-21 providesflow index, activity, density, induction time, and various molecularweight-related data for polymers produced when the co-catalyst isvaried. The base catalyst system studied in the data of Table 8 and FIG.13-21 is SC catalyst with 5 equivalents of DEALE per equivalent of Cr(designated herein as SC-500). The trend in flow index in Table 8indicates an increase in molecular weight upon addition of co-catalyst.Table 8 also demonstrates that catalyst activity is increased byco-catalyst addition. It should be noted that TEB (triethyl boron) canalso be used as a co-catalyst for SC catalysts. It should be understoodthat, co-catalyst is always added “in-reactor”, by definition.

TABLE 8 Effect of Co-Catalyst on SC-500 Catalyst Performance. BulkExample Time YIELD Flow Act.gPE/ Density Mw Mz Den. No. AdditionEquivalents (min) (g) Index gcat-1 hr (g/cc) Mn (× 10³) (× 10³) (× 10⁶)Mw/Mn Mz/Mw g/cc 28 none 0.00 54 158 49.0 487 0.43 0.9579 29 TEAL 2.0 eq65 157 31.9 649 0.44 9.6 217 1.68 22.6 7.8 0.9581 30 TEAL 5.0 eq 115 15633.3 368 0.37 7.7 196 1.56 25.3 8.0 0.9619 31 TIBA 2.0 eq 50 151 18.5873 0.44 8.7 240 1.89 27.4 7.9 0.9548 32 TIBA 5.0 eq 66 162 24.5 6860.37 8.5 210 1.69 24.6 8.0 0.9542 33 TNHAL 2.0 eq 57 155 17.3 811 0.438.6 241 1.97 28.0 8.2 0.9545 34 TNHAL 5.0 eq 60 151 30.5 619 0.33 7.6174 1.56 23.0 8.9 0.9516 [500 cc H2 present in all runs]

FIGS. 13 and 14 demonstrate a general increase in catalyst activity andmolecular weight, with a maximum effect at about 1-2 equivalents of Alper equivalent of Cr. Although not wishing to be bound by theory, it issuspected that higher levels of co-catalyst begin to poison the catalystat high levels. FIGS. 15-17 illustrate the effect of co-catalyst oninduction time. In all cases, it can be seen that activity peaks higherand largely remains higher when co-catalyst is present. Induction timesare essentially eliminated by the presence of co-catalyst for the SC-500system.

FIG. 18-21 demonstrate the effect of the presence of co-catalyst on themolecular weight distribution of the produced polymer. Although weobserved earlier that molecular weight was increased by co-catalyst,molecular weight distribution is largely unchanged. Additionally, theintensity of the high molecular weight shoulder, as indicated by theM_(Z)/M_(W) value is also unchanged relative to the polyethyleneproduced by SC-500 in the absence of co-catalyst. In summary,co-catalyst increases catalyst activity and polymer molecular weight forSC-500 catalyst, but polymer molecular weight distribution is largelyunchanged. These features are desirable for short residence timeoperation.

The same effect is seen with SC catalyst having 1.5 equivalentsDEALE/equivalent of Cr (designated herein as SC-150). Table 9 and FIG.22-28 provides induction time, activity, and various molecularweight-related data for polymers produced when the co-catalyst isvaried. The earlier observed trends for SC-500 are evident for SC-150.Induction times (see FIGS. 22-24) are virtually eliminated by theaddition of co-catalysts in these catalyst systems. FIG. 25-28demonstrate that molecular weight distribution is largely unaffected byco-catalyst. The intensity of the high molecular weight shoulder, asindicated by the M_(Z)/M_(W) value is also unchanged relative to thepolyethylene produced by SC-150 in the absence of co-catalyst. Tosummarize, co-catalyst increases catalyst activity for SC-150 catalyst,but polymer molecular weight distribution is largely unchanged.Therefore, judicious selection of co-catalyst allows one to modifymolecular weight and improve catalyst activity.

TABLE 9 Effect of Co-Catalyst on SC-150 Catalyst Performance. Act.gPE/Bulk Example Equiv- Time YIELD Flow gcat- Density Den. No. Additionalents (min) (g) Index 1 hr (g/cc) Mn (× 10³) Mw (× 10³) Mz (× 10⁶)Mw/Mn Mz/Mw g/cc 35 none 0.00 74 157 11.2 489 0.43 9.1 274 2.17 30.207.9 0.9502 36 TEAL 2.0 eq 57 155 15.3 608 0.38 9.0 265 1.99 29.28 7.50.9513 37 TIBA 2.0 eq 54 159 10.8 675 0.37 8.7 265 2.03 30.53 7.7 0.952438 TNHAL 2.0 eq 63 155 6.8 564 0.38 9.6 328 2.13 34.07 6.5 0.9522 [500cc H2 added to all runs]

Co-catalyst addition also has beneficial effects on CrOx catalysts.Table 10 and FIG. 29-34 provide data demonstrating the effect ofco-catalyst on the performance of Ti—CrOx (on Grace 955 silica). Table10 demonstrates that flow index decreases upon addition of TEAL andtherefore polymer molecular weight is increased by the use of 5 eq.co-catalyst for the Ti—CrOx catalyst. Ti—CrOx activity respondssimilarly to co-catalyst as does SC-500 and SC-150 catalyst discussedabove.

TABLE 10 Effect of Co-Catalyst on Ti—CrOx Catalyst Performance. BulkExample Equiv- Time YIELD Flow Act.gPE/ Density Mw Mz Den. No. Additionalents (min) (g) Index gcat-1 hr (g/cc) Mn (× 10³) (× 10³) (× 10⁶) Mw/MnMz/Mw g/cc 39 none 0.00 62 156 3.8 1,497 0.32 12.6 212 0.88 16.9 4.20.9466 40 TIBA 2.0 eq 40 152 4.4 2,135 0.26 9.3 268 1.82 28.9 6.8 0.947541 TIBA 5.0 eq 88 139 2.0 915 0.30 7.8 319 2.01 41.0 6.3 0.9457 42 TNHAL2.0 eq 43 159 3.9 2,474 0.25 9.0 247 1.41 27.6 5.7 0.9464 43 TNHAL 5.0eq 120 135 1.4 561 0.35 8.8 439 2.37 50.1 5.4 0.9493 44 TEAL 2.0 eq 36155 6.7 2,276 0.29 9.0 217 1.19 24.2 5.5 0.9471 45 TEAL 5.0 eq 80 1482.6 937 0.29 8.4 297 1.84 35.2 6.2 0.9472 [500 cc H2 present in allruns]

An improvement in activity is seen, particularly at 1-2 eq of Al per eqof Cr. As seen in FIGS. 31-34, molecular weight distribution broadenswhen co-catalyst is present, and a pronounced high molecular weightshoulder does not develop. Broadening of the polymer molecular weightdistribution will improve physical properties without increasing polymerswell.

Additionally, the inventors have discovered that various co-catalystsnot based on aluminum are also useful in the present invention. Forexample, TEB (triethyl boron) was studied for its effect on catalystperformance. Table 11 demonstrates the effect on performance of TEBco-catalyst on CrOx (chromium oxide on Grace 955 silica) and Ti—CrOxcatalyst systems.

TABLE 11 Effect of Co-Catalyst on CrOx and Ti—CrOx Catalyst Performance.Act.gPE/ Bulk Example H2 Time YIELD Flow gcat- Density Mn Mw Mz No.Addition eq. (scc) (min) (g) Index 1 hr (g/cc) (× 10³) (× 10³) (× 10⁶)Mw/Mn Mz/Mw Den. g/cc CrOx on 955 Silica 46 none 79 174 2.4 1,250 0.3226.4 268 1.33 10.1 5.0 0.9425 47 TEB 2.0 eq 56 158 1.8 1,832 0.32 0.948048 none 500 82 161 6.8 1,347 0.33 21.6 217 1.06 10.0 4.9 0.9407 49 TEB2.0 eq 500 58 155 8.9 1,574 0.28 15.3 275 1.60 18.0 5.8 0.9463 TiCrOx on955 Silica 50 none 32 161 11.9 2,563 0.20 10.5 172 0.88 16.4 5.1 0.945651 TEB 2.0 eq 56 149 5.1 1,449 0.32 6.2 197 1.28 31.7 6.5 0.9522 52 nonenone 500 64 175 9.7 1,380 0.32 9.8 182 0.81 18.5 4.5 0.9471 53 TEB 2.0eq 500 48 152 21.3 1,589 0.33 6.4 177 1.41 27.4 8.0 0.9534

FIG. 35-36 illustrate molecular weigh-related data for polyethyleneproduced from Ti—CrOx catalyst alone (FIG. 35), and Ti—CrOx with TEBco-catalyst (FIG. 36). Polymer molecular weight is increased as seen inthe decrease in flow index upon the use of TEB in comparison to noco-catalyst for both CrOx and Ti—CrOx systems in the absence ofhydrogen. Catalyst activity was largely unaffected in both catalystsystems by the use of TEB, however, TEB broadens molecular weightdistribution. Additionally, the broadening of molecular weightdistribution effected by the use of TEB appears accompanied by thegrowth of only a modest molecular weight shoulder (FIG. 36) as is thecase when using DEALE as co-catalyst.

The present invention allows for the manipulation of molecular weight,molecular weight distribution, catalyst activity, as well as otherproperties of the resulting polyethylene through the judicious use ofco-catalyst generally, and of aluminum alkyl co-catalysts specifically.The aluminum alkyl compounds expressly discussed herein are discussed byway of non-limiting example only; other aluminum alkyls are alsoapplicable in and a part of the present invention. Similarly, alkylaluminum alkoxides other than DEALE are also applicable in the presentinvention. These include, but are not limited to diethyl aluminumethoxide, dimethyl aluminum ethoxide, dipropyl aluminum ethoxide,diethyl aluminum propoxide, and methyl ethyl aluminum ethoxide. Throughjudicious use of the co-catalyst, one may modify these properties andtailor the resulting polymer for specific applications. Importantly, theinvention provides for the production of high molecular weightpolyethylenes with chromium-based catalysts of high activities,resulting in the ability to run at shorter reactor residence times. Thisaffords improvements in the space time yield for polyethylene productionusing chromium-based catalysts while maintaining high reactiontemperatures.

Fluid Bed Gas Phase Examples

The following provides fluid bed gas phase examples of the presentinvention. A gas phase fluidized bed polymerization reactor of theUNIPOL™ process design having a nominal diameter of 14 inches was usedfor the continuous production of high-density ethylene-hexene copolymer.In these cases, the cycle gas blower was situated upstream of the cyclegas heat exchanger in the gas recirculation loop but the two could havebeen reversed to reduce the gas temperature where it entered the heatexchanger. The cycle pipe was about 2 inches in diameter and its flowrate was manipulated by a ball valve in the cycle line to control thesuperficial gas velocity in the fluid bed at the desired rate. Monomersand gaseous components were added upstream of the cooler before theblower, at the blower impeller or after the blower. Dry catalyst wascontinuously added in discrete small aliquots via ⅛ inch tube directlyto the fluidized bed at a height about 0.1 to 2 m above the distributorplate and most preferably at about the 0.2 to 1.2 m range using anitrogen carrier gas flow at a location about 15 to 50% of the reactordiameter. Polymer product was withdrawn periodically from the reactorthrough a discharge isolation tank in aliquots of about 0.2 to 5 kg tomaintain a desired approximate average fluidized bed level or weight. Adilute stream of oxygen in nitrogen (200 ppmv) was available and used onsome experiments to manipulate the polymer molecular weight andmolecular weight distribution. It was added to the cycle gas before theheat exchanger when no free aluminum alkyl was present in the reactionsystem, but its addition point was switched to the fluidized bed whenfree TEAL and DEALE were present in order to avoid the possibility ofsome of the oxygen reacting with the aluminum alkyl in the cycle line orheat exchanger before entering the fluid bed. This was a precaution anddoes not preclude its addition to the cycle line or before the heatexchanger.

Various sets of experiments were conducted at discrete times, and eachset included a comparative case. Background impurities in the feedstreamand in the reactors varied with time and caused minor shifts in reactiontemperature and catalyst productivity between experimental sets.Comparative cases include catalyst prepared at a commercialmanufacturing facility as well as catalysts prepared in thelaboratories. The laboratory-prepared catalysts required a lowerreaction temperature and provided a comparative case for experimentalcatalysts also prepared in the laboratory.

Examples 54 through 59 in Table 12 show the results of employing varioussupports and chromium sources. The reactor operated well withoutsheeting or chunk formation for all the examples. Examples 54 and 55show the results for the comparative catalyst (silylchromate made on 955silica dehydrated at 600° C. and reduced with 5 equivalents of DEALE).The experimental catalysts are compared to Example 55. SC catalyst madeon MS3050 support (Example 56) had significantly higher catalystproductivity and made broad molecular weight distribution polymer with ahigh molecular weight shoulder. The catalyst employed in Examples 57 and58 are based on CrOx on 955 silica activated at 825° C. and then reducedwith 5 equivalents of DEALE. In both cases higher catalystproductivities were obtained and higher reaction temperatures wererequired to make the polymer. This shows that the catalysts inherentlymake higher molecular weight polymer and will be useful for shortresidence time operation. In Example 58, oxygen addback to the reactorwas also used which at a given temperature lowers the polymer molecularweight and increases the polymer melt flow ratio (MFR) values(indicative of broader polymer molecular weight distribution). Example59 shows the results for a PQ CrOx catalyst (CrOx on MS3050) activatedat 700° C. followed by reduction with 5 equivalents of DEALE. Here againhigher catalyst productivities are obtained and higher reactiontemperatures are needed to make the polymer.

In summary, these gas phase results support the observations found inthe earlier examples. Higher catalyst productivities and highermolecular weight polymers can be achieved employing alternate supportsfor silylchromate catalyst production. Employment of reduced CrOxcatalysts can also supply the same improvements. In all cases broadmolecular weight polymers are obtained with the desirable high molecularweight shoulder.

TABLE 12 Gas Phase Conditions and Results with DEALE In-Catalyst; SilicaSupport Varied Example 54 55 Comparative Comparative 56 57 58 59 CrSource Silyl Silyl Silyl Chromium Chromium Chromium Chromate ChromateChromate Oxide Oxide Oxide Cr Loading, wt % 0.24 0.24 0.50 0.50 0.500.50 DEALE/Cr Mole 5 5 5 5 5 5 Ratio Silica Support 955 955 MS 3050 955955 MS 35100 Source (Comm. = Commercial) Comm. Pilot Plant Pilot PlantTemperature, ° C. 96.5 88.0 92.1 103.9 99.9 104.9 Total Pressure, kPa2501 2492 2501 2494 2493 2490 Ethylene Pressure, 1524 1510 1517 15101510 1517 kPa H₂/C₂ Mole Ratio 0.0097 0.0103 0.0106 0.0103 0.0204 0.0106Hexene/C₂ Mole 0.0049 0.0100 0.0079 0.0050 0.0065 0.0031 Ratio OxygenAddition, None None None None 0.10 0.251 ppmv Superficial Gas 0.5300.530 0.530 0.589 0.607 0.527 Velocity, m/sec Bed Weight, kg 83.9 83.971.7 79.4 79.4 69.9 Bed Height, m 2.18 2.02 2.60 2.08 2.09 3.48Production Rate, kg/h 16.3 16.3 11.3 14.1 12.7 15.0 Average Residence5.2 5.1 6.3 5.7 6.0 4.6 Time, h Space TimeYield, 83 91 50 75 70 50kg/h/m³ Catalyst Productivity, 4965 4035 7217 6554 5748 6375 kg/kgFluidized Bulk 325 351 232 322 320 170 Density, kg/m³ Settled BulkDensity, 487 527 352 492 508 311 kg/m³ Resin APS, mm 0.716 0.734 1.110.777 0.777 0.919 Melt Index (I₂), 0.10 0.08 0.10 0.12 0.09 0.05 dg/minFlow Index (I₅), 0.49 0.47 0.60 0.60 0.49 0.44 dg/min Flow Index (I₂₁),10.5 12.8 13.6 12.3 12.1 4.16 dg/min MFR (I₂₁/I₅) 21.2 27.2 22.5 20.624.7 9.4 MFR (I₂₁/I₂) 107 155 131 99 138 90.9 Density, g/cm³ 0.94720.9481 0.9482 0.9479 0.9483 0.9485 Mn 10214 — 8374 10283 11140 14958 Mw256077 — 291804 187522 206907 304972 Mz 1734620 — 2100445 12138611302183 1779473 Mz + 1 3284606 — 3626163 2681581 2673316 3271683 Mv175935 — 190696 134078 146591 216325 PDI (Mw/Mn) 25.07 — 34.85 18.2418.57 20.39 PDI (Mz/Mw) 6.77 — 7.20 6.47 6.29 5.83 CHMS (% > 500K) 11.76— 13.29 8.62 9.93 14.28 CLMS (% < 1K) 1.76 — 2.24 1.95 1.44 0.98

Examples 60 through 64 in Table 13 were run in a reactor similar tothose of Table 12. Example 60 is the comparative example. Examples 61through 64 show the effect of TEAL addition to a standard silylchromatecatalyst (silylchromate made on 955 silica dehydrated at 600° C. andreduced with 5 equivalents of DEALE). In Table 13 the results show anoptimum in the amount of TEAL added to a gas phase fluid bedpolymerization of silylchromate catalyst based on productivity, resinparticle characteristics, increased reaction temperature and MFR. Forthe specified catalyst and reaction conditions, that optimum wasapproximately in the 0.5 to 3 TEAL/Cr range and more preferably in the 1to 2 TEAL/Cr range. The catalyst was the same in this set ofexperiments. The productivity values were based on a catalyst additionrate and resin production rate material balance. The chromium remainingin the resin is similar to the productivity trends. The TEAL/Cr addedmole ratio was based on the TEAL feed rate and a measure of the Cr inthe resin by an X-ray method. The TEAL was added to the bed using a⅛-inch tube set up like the catalyst injection tube but without sweepnitrogen. The TEAL was provided as a dilute solution in purifiedisopentane, and the container it was prepared in had previously beenexposed to TEAL prior to filling to reduce the possibility of reactiveimpurities such as water in the container that would consume the smallamount of TEAL present. The reactor operated well during the time TEALwas added without sheet, chip or chunk formation. The static voltage inthe bed measured by a high resistance-high capacitance electronic probeshowed reduced levels when TEAL was present—the static remained neutralbut in a narrower band. The wall skin thermocouples located at variousdistances above the plate in the fluid bed and in the freeboard abovethe bed were excellent for the no-TEAL case and seemed even better inthe presence of TEAL with less fluctuation and a shift of about 1 to 2°C. closer (from below) towards the bed average core temperature.

In summary the addition of co-catalyst (TEAL) results in higher catalystactivity and allows the reactor to run at higher temperatures to achievethe same polymer molecular weight. The polymer molecular weightdistribution remains unchanged in all these examples.

TABLE 13 Gas Phase Conditions and Results with DEALE In-Catalyst;TEAL/Cr Ratio Varied Experiment 60 Comparative 61 62 63 64 Cr SourceSilyl Silyl Silyl Silyl Silyl Chromate Chromate Chromate ChromateChromate Cr Loading, wt % 0.24 0.24 0.24 0.24 0.24 DEALE/Cr Mole Ratio 55 5 5 5 Silica Support 955 955 955 955 955 Source (Comm. = Commercial)Comm. Comm. Comm. Comm. Comm. TEAL Added to Reactor, None 0.91 2.22 3.224.85 TEAL/Cr Mole Ratio Temperature, ° C. 98.0 102.5 102.5 102.5 100.5Total Pressure, kPa 2491 2492 2490 2492 2491 Ethylene Pressure, kPa 15101510 1510 1510 1510 H₂/C₂ Mole Ratio 0.010 0.010 0.010 0.010 0.099Hexene/C₂ Mole Ratio 0.00433 0.00353 0.00330 0.00331 0.00360 OxygenAddition, ppmv None None None None None Superficial Gas Velocity, 0.5550.561 0.555 0.564 0.564 m/sec Bed Weight, kg 88.9 87.5 87.5 87.5 87.1Bed Height, m 3.04 2.94 3.05 3.12 3.21 Production Rate, kg/h 19.1 18.017.4 16.6 17.2 Average Residence Time, h 4.7 4.9 5.0 5.3 5.1 Space-TimeYield, 70 69 64 59 61 kg/h/m³ Catalyst Productivity, 5041 6666 6452 61505308 kg/kg Fluidized Bulk Density, 328 333 320 315 304 kg/m³ SettledBulk Density, 483 485 466 464 447 kg/m³ Resin APS, mm 0.752 0.790 0.7800.765 0.681 Resin Fines <120 Mesh, 1.31 1.28 0.39 0.65 0.82 wt % MeltIndex (I₂), dg/min 0.096 0.098 0.098 0.090 0.087 Flow Index (I₅), dg/min0.470 0.474 0.472 0.459 0.450 Flow Index (I₂₁), dg/min 9.79 9.75 9.919.81 10.2 MFR (I₂₁/I₅) 20.7 20.5 21.1 21.3 22.7 MFR (I₂₁/I₂) 102 100 101108 116 Density, g/cm³ 0.9480 0.9481 0.9474 0.9474 0.9472 Cr in Polymer,ppmw 0.44 0.35 0.38 0.41 0.53 Mn 12460 13519 11758 9685 11647 Mw 279637265684 276778 263471 253762 Mz 1875317 1598806 1826871 1722578 1731498Mz + 1 3543254 3109360 3432220 3224517 3436515 Mv 193220 188165 190700182352 174394 PDI (Mw/Mn) 22.4 19.65 23.54 27.2 21.79 PDI (Mz/Mw) 6.716.02 6.60 6.54 6.82 CHMS (% > 500K) 12.63 12.82 13.01 12.24 11.98 CLMS(% < 1K) 1.31 1.12 1.34 2.48 1.27

The experiments of Examples 65-73 (summarized in Table 14) and Example74 (discussed in the text below) were conducted in gas phasepolymerization reactors similar to those of the previous experiments.Examples 65 through 71 examined the effects of TEAL co-catalyst additionin the preferred range at high and low space-time yield and withcatalysts prepared at two DEALE/Cr catalyst levels (5 equivalents ofDEALE/Cr and 1.5 equivalents of DEALE/Cr). TEAL increased the catalystproductivity about 35% at each STY studied, and also increased thereaction temperature about 3 to 5° C. at each space-time yield. TEALallowed operation at the higher space-time yield with catalystproductivity comparable or greater than that of the lower space-timeyield without TEAL. Resin particle size was increased and fines reducedwhen operating at the higher space-time yield in the presence of TEALcompared to without it. MFR increased with increasing space-time yield.The performance of the low and high DEALE catalysts was similar in thepresence of TEAL but different without. As can be seen the catalystproductivity and required reactor temperature are inadequate at highspace-time yield (low residence times) operation without the presence ofco-catalyst (Ex. 67 and 70). These gas phase results support the earlierexamples showing the use of co-catalyst in conjunction withsilylchromate catalysts.

Example 72 shows the use of oxygen add-back with the addition ofco-catalyst. Polymer flow index increased upon the addition of oxygen tothe reactor. Oxygen can be added to control polymer molecular weight andmolecular weight distribution.

DEALE was added to the reactor in Example 73 instead of TEAL using ahigher loaded chromium oxide catalyst (0.5wt % Cr on 955 silicaactivated at 825° C.), resulting in increased catalyst productivity andincreased reaction temperature compared to standard silylchromateoperation with or without TEAL.

Example 74: Addition of TEAL to an ongoing polymerization reaction usinga low DEALE/Cr ratio silylchromate catalyst (1.5:1 DEALE/Cr) in thefluidized bed twice resulted in the formation of polymer sheets andagglomerates that blocked the resin discharge port forcing a reactorshutdown

The reactor operated well for Experiments 65 to 72. TEAL was introducedto a TEAL-free system successfully using the 5:1 DEALE/Cr silylchromatecatalyst. TEAL examples with the 1.5:1 DEALE/Cr catalyst weresuccessfully conducted by transitioning from the 5:1 to 1.5:1 catalystwith TEAL already present in the fluidized bed reactor. It is preferredto initiate the catalyst addition, particularly for the lower DEALE/Crcatalysts, to a bed that already contains a sufficient amount of TEAL.

The TEAL and DEALE addition to the reactors were made at apre-calculated rate and then the Al/Cr ratio calculated when theexperiment was finished. It would be possible to control at apredetermined Al/Cr ratio based on catalyst addition rate, or to specifyan approximate constant feed rate of the TEAL or DEALE. Their feed ratecould also be proportioned to the resin production rate to control theirconcentration at some specified level, preferably one that achieves thedesired results with the minimum use of reactive agent.

TABLE 14 Gas Phase Conditions and Results with DEALE In-Catalyst;DEALE/Cr Ratio Varied Example 65 67 Comparative 66 Comparative 68 CrSource Silyl Chromate Silyl Chromate Silyl Chromate Silyl Chromate CrLoading, wt % 0.24 0.24 0.24 0.24 DEALE/Cr Mole Ratio 5 5 5 5 SilicaSupport 955 955 955 955 Source (Comm. = Commercial) Comm. Comm. Comm.Comm. TEAL Added to Reactor, None 0.91 None 1.07 TEAL/Cr Mole RatioTemperature, ° C. 98.0 102.5 92.7 99.0 Total Pressure, kPa 2491 24922489 2488 Ethylene Pressure, kPa 1510 1510 1441 1510 H₂/C₂ Mole Ratio0.010 0.010 0.0544 0.0101 Hexene/C₂ Mole Ratio 0.00433 0.00353 0.00650.0036 Oxygen Addition, ppmv None None None None Superficial GasVelocity, 0.555 0.561 0.552 0.567 m/sec Bed Weight, kg 88.9 87.5 90.389.4 Bed Height, m 3.04 2.94 2.97 2.92 Production Rate, kg/h 19.1 18.034.0 33.7 Average Residence Time, h 4.7 4.9 2.7 2.7 Space-Time Yield,kg/h/m3 70 69 128 130 Catalyst Productivity, kg/kg 5041 6666 2786 3618Fluidized Bulk Density, 328 333 343 346 kg/m³ Settled Bulk Density,kg/m³ 483 485 523 511 Resin APS, mm 0.752 0.790 0.655 0.752 Resin Fines<120 Mesh, 1.31 1.28 1.33 0.90 wt % Melt Index (I₂), dg/min 0.096 0.0980.083 0.081 Flow Index (I₅), dg/min 0.470 0.474 0.438 0.441 Flow Index(I₂₁), dg/min 9.79 9.75 10.4 10.1 MFR (I₂₁/I₅) 20.7 20.5 23.5 23.0 MFR(I₂₁/I₂) 102 100 125 126 Density, g/cm³ 0.9480 0.9481 0.9471 0.948 Cr inPolymer, ppmw 0.44 0.35 0.80 0.59 Mn 12460 13519 8229 10657 Mw 279637265684 271033 230657 Mz 1875317 1598806 1888749 1607038 Mz + 1 35432543109360 3520335 3596324 Mv 193220 188165 183560 160356 PDI (Mw/Mn) 22.419.65 32.94 21.64 PDI (Mz/Mw) 6.71 6.02 6.97 6.97 CHMS (% > 500K) 12.6312.82 12.45 10.95 CLMS (% < 1K) 1.31 1.12 2.68 1.57 Example 70 69Comparative 71 72 73 Cr Source Silyl Silyl Silyl Silyl Chromium ChromateChromate Chromate Chromate Oxide Cr Loading, wt % 0.24 0.24 0.24 0.240.50 DEALE/Cr Catalyst 1.5 1.5 1.5 5 0 Mole Ratio Silica Support 955 955955 955 955 Source (Comm. = Commercial) Comm. Comm. Comm. Comm. Comm.TEAL Added to 2.47 no 0.83 1.60 DEALE at 4.7 Reactor, Al/Cr TEAL/Cr MoleRatio Temperature, ° C. 102.0 96.7 100.0 102.0 104.5 Total Pressure, kPa2491 2488 2488 2489 2491 Ethylene Pressure, kPa 1510 1503 1510 1510 1517H₂/C₂ Mole Ratio 0.010 0.010 0.0101 0.010 0.0098 Hexene/C₂ Mole Ratio0.0037 0.0042 0.0036 0.0037 0.0034 Oxygen Addition, ppmv None None None0.120 None Superficial Gas 0.570 0.564 0.573 0.570 0.564 Velocity, m/secBed Weight, kg 88.5 90.3 88.9 87.5 84.8 Bed Height, m 3.22 3.00 2.923.42 2.84 Production Rate, kg/h 19.3 32.8 34.7 18.9 14.9 AverageResidence 4.6 2.7 2.6 4.6 5.7 Time, h Space-Time Yield, 67 123 133 62 59kg/h/m³ Catalyst Productivity, 6640 2564 3871 4926 17500 kg/kg FluidizedBulk Density, 309 338 343 288 335 kg/m³ Settled Bulk Density, 476 508498 461 418 kg/m³ Resin APS, mm 0.770 0.617 0.757 0.665 1.22 Resin Fines<120 Mesh, 0.73 1.62 0.64 1.14 0.56 wt % Melt Index (I₂), dg/min 0.0820.085 0.088 0.101 0.067 Flow Index (I₅), dg/min 0.429 0.43 0.46 0.5030.39 Flow Index (I₂₁), dg/min 8.83 9.60 10.3 10.5 9.60 MFR (I₂₁/I₅) 20.622.0 22.4 21.0 24.8 MFR (I₂₁/I₂) 104 110 115 103 143.1 Density, g/cm³0.9469 0.9478 0.9473 0.9481 0.9463 Cr in Polymer, ppmw — — — — — Mn11571 11696 14938 9281 24787 Mw 254022 256144 232504 218079 235551 Mz1560945 1450341 1326253 1364031 1350517 Mz + 1 2925600 2717358 25627732544778 3047628 Mv 178701 182668 167657 152554 175124 PDI (Mw/Mn) 21.9521.9 15.56 23.5 9.5 PDI (Mz/Mw) 6.14 5.66 5.70 6.25 5.73 CHMS (% > 500K)12.14 12.74 11.25 10.47 10.9 CLMS (% < 1K) 1.63 1.43 0.75 2.25 0.08

Although the present invention and its advantages have been described indetail, it should be understood that various changes, substitutions andalterations can be made herein without departing from the spirit andscope of the invention as defined by the appended claims. Moreover, thescope of the present application is not intended to be limited to theparticular embodiments described in the specification. As one ofordinary skill in the art will readily appreciate from the disclosure ofthe present invention, processes, machines, manufacture, compositions ofmatter, means, methods, or steps, presently existing or later to bedeveloped that perform substantially the same function or achievesubstantially the same result as the corresponding embodiments describedherein may be utilized according to the present invention. Accordingly,the appended claims are intended to include within their scope suchprocesses, machines, manufacture, compositions of matter, means,methods, or steps.

1. A process for producing an ethylene polymer comprising the steps of:contacting ethylene under polymerization conditions with a catalystsystem in a reactor, said catalyst system comprising a supportedchromium catalyst comprising chromium oxide, an alkyl aluminum alkoxideor an alkyl aluminum alkoxide in combination with an alkyl aluminum, anda silica-containing support comprising silica selected from the groupconsisting of silica having: (a) a pore volume of about 1.1 to about 1.8cm³/g and a surface area of about 245 to about 375 m²/g, (b) a porevolume of about 2.4 to about 3.7 cm³/g and a surface area of about 410to about 620 m²/g, and (c) a pore volume of about 0.9 to about 1.4 cm³/gand a surface area of about 390 to about 590 m²/g; b) wherein thesupported chromium catalyst is activated at about 400 to about 860° C.;and c) wherein at least a portion of the alkyl aluminum alkoxide or thealkyl aluminum oxide in combination with the alkyl aluminum is added insitu, such that the portion of the alkyl aluminum alkoxide or the alkylaluminum oxide in combination with the alkyl aluminum is added into thereactor in the presence of the monomers under polymerization conditions,and is not combined with the supported chromium catalyst prior to theaddition into the reactor; wherein the alkyl aluminum oxide is presentin an amount such that the polymer side chain branching, of theresulting ethylene polymer is reduced as compared to an ethylene polymerproduced under identical conditions in the absence of the alkyl aluminumalkoxide, and wherein the alkyl aluminum alkoxide is present in anamount to effect a final molar ratio of aluminum to chromium of fromabout 0.1:1 to 10:1.
 2. The process of claim 1 wherein said alkylaluminum is triethyl aluminum, tri-isobutyl aluminum, or tri-n-hexylaluminum.
 3. The process of claim 1 wherein said alkyl aluminum alkoxideis diethyl aluminum ethoxide.
 4. The process of claim 1, wherein saidcatalyst system further comprises titanium tetraisopropoxide.
 5. Theprocess of claim 1 wherein said polymerization is gas phasepolymerization.
 6. The process of claim 3 wherein said addition ofdiethyl aluminum ethoxide comprises addition directly to the catalystduring catalyst preparation.
 7. The process of claim 1 wherein thepolymer M_(w)/M_(n) is greater than or equal to 16 and the polymerM_(z)/M_(w) is greater than or equal to
 6. 8. The process of claim 1,wherein the alkyl aluminum alkoxide has the general formula: R₂—Al—OR,wherein each of the alkyl groups R may be the same or different, andwherein the alkyl groups R have from 1 to about 12 carbon atoms.
 9. Theprocess of claim 1, wherein the alkyl aluminum alkoxide is selected fromthe group consisting of diethyl aluminum ethoixide, diethyl aluminummethoxide, dimethyl aluminum ethoxide, di-isopropyl aluminum ethoxide,diethyl aluminum propoxide, di-isobutyl aluminum ethoxide, methyl ethyalaluminum ethoxide, and combinations thereof.
 10. The process of claim 1,wherein the alkyl aluminum has the general formula: R₃Al, wherein eachof the alkyl groups R may be the same or different, and wherein thealkyl groups R have from 1 to about 12 carbon atoms.
 11. The process ofclaim 1, wherein the alkyl aluminum is selcted from the group consistingtriethyalaluminum, triisopropylaluminum, tri-isobutylaluminum,tri-n-hexyl aluminum, methyal diethylaluminum, trimethylaluminum andcombinations thereof.